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EP1148571B1 - Method for recycling and treating of salt and alkaline batteries - Google Patents

Method for recycling and treating of salt and alkaline batteries Download PDF

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Publication number
EP1148571B1
EP1148571B1 EP20010108707 EP01108707A EP1148571B1 EP 1148571 B1 EP1148571 B1 EP 1148571B1 EP 20010108707 EP20010108707 EP 20010108707 EP 01108707 A EP01108707 A EP 01108707A EP 1148571 B1 EP1148571 B1 EP 1148571B1
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EP
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Prior art keywords
ferrous
recycling
batteries
zinc
fraction
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EP20010108707
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German (de)
French (fr)
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EP1148571A1 (en
Inventor
André 't Serstevens
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Revatech SA
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Revatech SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to a method for recycling salt and alkaline cells of all sizes, allowing the recovery of most of their constituents, whether mixed or not: in addition, the process tolerates the presence, in limited proportion , lithium batteries, nickel / cadmium and nickel-hydride batteries and button cells.
  • This recycling process comprises a succession of three phases: the sorting of batches of harvested piles, the mechanical treatment of the piles and the physical and / or physicochemical treatment of the by-products obtained during the second phase.
  • the recycling process comprises a succession of three phases.
  • the figure 1 represents the diagram of the sorting operations.
  • the figure 2 represents the diagram of mechanical and physical treatments.
  • the figure 3 represents the physico-chemical treatment diagram.
  • the figure 4 represents the diagram of the sorting and mechanical processing unit.
  • the figure 5 represents the diagram of the acidic washing unit of plastics.
  • the figure 6 represents the diagram of the zinc and manganese extraction and recovery unit
  • the physico-chemical treatment unit can be divided into two parts. The first is used to carry out the acid wash of the fraction called "plastics". The second allows recycling and recovery of zinc and manganese batteries by the hydrometallurgical treatment of the "BM".

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the recycling of salt and alkaline batteries of all sizes and types comprises a three stage scheme of sorting, mechanical treatment and hydrometallurgical treatment. A process for the recycling of batteries of all sizes comprises a three stage succession : (a) a primary phase for the sorting of collected batteries ; (b) a second phase of mechanical treatment of the batteries by milling, magnetic separation of the milled product, granular fractionation of the non-ferrous milled material and qualitative separation of the large particles ; 7 fractions are separated designated : ferrous, fines, medium, rebus, non-ferrous, plastics and paper ; (c) a third phase of physical or physico-chemical treatment of the fractions, the ferrous and no-ferrous being valorized and the plastics fraction being washed in H2SO4 and HNO3 and drained. The process is characterized in that, in the third phase the middle fraction is re-milled and integrated with the fine fraction to form a Black Mass group ; this is submitted to a hydrometallurgical treatment comprising the stages : (i) caustic soda wash; (ii) filtration and rinsing to extract chlorides, ammonium, potassium and other soluble salts ; (iii) acid attack by H2SO4 solution in the presence of Fe to dissolve Zn and Mn ; (iv) reduction of the group by H2O2 in the presence of an antifoam agent to dissolve residual Mn ; (v) adjustment of pH by ammonia, ZnO or MnO2 ; (vi) flocculation of the group, allowing separation of a solution rich in sulfates of Zn and Mn; (vii) purification of the solution by adjustment of pH with H2SO4; (viii) cementation of Cu, Cd, Hg, and Pb with Zn powder and elimination by filtration ; (ix) complexation of Ni with sodium or potassium ethylxanthate after pH adjustment and filtration ; and (x) valorization of sulfates of Zn and Mn in solution or after precipitation.

Description

L'invention concerne un procédé de recyclage des piles salines et alcalines de toutes dimensions, permettant la valorisation de la plus grande partie de leurs constituants, qu'elles soient en mélange ou non : en outre, le procédé tolère la présence, en proportion limitée, de piles au lithium, d'accumulateurs nickel/cadmium et nickel-hydrures et de piles boutons. Ce procédé de recyclage comporte une succession de trois phases : le tri des lots de piles récoltées, le traitement mécanique des piles et le traitement physique et/ou physico-chimique des sous-produits obtenus lors de la deuxième phase.The invention relates to a method for recycling salt and alkaline cells of all sizes, allowing the recovery of most of their constituents, whether mixed or not: in addition, the process tolerates the presence, in limited proportion , lithium batteries, nickel / cadmium and nickel-hydride batteries and button cells. This recycling process comprises a succession of three phases: the sorting of batches of harvested piles, the mechanical treatment of the piles and the physical and / or physicochemical treatment of the by-products obtained during the second phase.

De nos jours, la protection de l'environnement est devenue une préoccupation majeure voire une obligation. Vu la présence de produits toxiques ou dangereux tels que le mercure, le plomb, le zinc, le nickel ou encore le cadmium dans les piles et batteries électriques, il est apparu indispensable de proposer des solutions de traitement et de valorisation pour ce type de déchets. Ceux-ci sont maintenant collectés plutôt qu'éliminés en décharge comme de simples déchets ménagers . Depuis longtemps déjà. les batteries au plomb et au nickel-cadmium font l'objet d'un traitement approprié qui conduit au recyclage de leurs composants. Vu leur composition et leur forme très variées, le traitement des autres piles. principalement alcalines et salines, est plus complexe. Plusieurs procédés ont déjà été proposés. Les plus anciens nécessitent une étape de calcination ou de pyrolyse qui rend les opérations longues et coûteuses. D'autres exploitent ia voie pyrométallurgique (Citron. Valdi). D'autres encore, plus récents, soumettent le matériau broyé à une lixiviation en milieu soit acide soit basique, suivi d'un traitement électrolytique ou non de l'une ou l'autre des fractions obtenues (ex. Eurodieuze, Recupyl. Zimaval).Today, the protection of the environment has become a major concern, even an obligation. Given the presence of toxic or dangerous products such as mercury, lead, zinc, nickel or cadmium in electric cells and batteries, it has become essential to provide treatment and recovery solutions for this type of waste. . These are now collected rather than disposed of in landfills as simple household waste. For a long time already. lead and nickel-cadmium batteries are suitably treated to recycle their components. Given their composition and shape very varied, the treatment of other batteries. mainly alkaline and saline, is more complex. Several processes have already been proposed. The older ones require a calcination or pyrolysis step that makes operations time consuming and expensive. Others exploit the pyrometallurgical route (Citron Valdi). Still others, more recent, subject the crushed material to leaching in either acidic or basic medium, followed by electrolytic treatment or not of any of the fractions obtained (eg Eurodieuze, Recupyl, Zimaval). .

La présente invention se distingue des procédés précédemment cités de la façon qui suit

  1. 1° elle ne fait intervenir aucune opération thermique qui rend le procédé souvent très coûteux tant à la mise en oeuvre qu'à l'exploitation
  2. 2° elle soumet le matériau broyé à une lixiviation acide et réductrice qui permet de solubiliser, dans leur totalité, le manganèse et le zinc présents dans les piles salines et alcalines
  3. 3° elle ne fait intervenir aucun traitement électrolytique dont l'exploitation est souvent très complexe à gérer avec des produit de composition très variable et qui ne peuvent garantir ni la production de produits finis de qualité, ni un rendement énergétique stable.
The present invention differs from the aforementioned methods in the following way
  1. 1 ° it does not involve any thermal operation that makes the process often very expensive both for implementation and operation
  2. 2 ° it subjects the crushed material to acidic and reducing leaching which solubilizes, in their entirety , the manganese and the zinc present in the saline and alkaline cells
  3. (3) it does not involve any electrolytic treatment whose operation is often very complex to manage with products of very variable composition and which can not guarantee either the production of finished products of quality, nor a stable energy yield.

Le procédé de recyclage comporte une succession de trois phases.The recycling process comprises a succession of three phases.

La première phase se déroule en deux étapes.
La première étape consiste en un tri manuel sur bande transporteuse, assurant l'élimination des corps étrangers et des piles indésirables.
La deuxième étape est le criblage mécanique de la masse pour la récupération des piles boutons.
A l'issue de la première phase, on a d'une part. les piles alcalines et salines et d'autre part les piles boutons, les corps étrangers et autres piles indésirables qui sont orientés vers des filières de traitement adéquates.
La deuxième phase est constituée par le traitement mécanique des piles comportant les opérations suivantes

  • le broyage mécanique des piles ; ce broyage, à sec, s'effectue par un broyeur/concasseur qui peut être soit un broyeur rotatif à marteaux ou à barreaux mobiles, soit un broyeur à percussions ou encore un broyeur cisaille. En fait. n'importe quel type de broyeur peut être choisi . à condition qu'il réduise les piles considérées en fragments de 0 à 15/20 mm.
  • la séparation magnétique du broyât au moyen soit d'un overband, soit d'un tambour magnétique pour en extraire les fragments de métaux ferreux qui seront appelés ultérieurement les « ferreux ».
  • le fractionnement granulométrique du broyât déferraillé ; le broyat est divisé en trois catégories :
    • les particules de plus grandes dimensions ou supérieures à 5 mm appelées « gros »
    • les particules de dimensions intermédiaires ou comprises entre 3 et 5 mm appelées « moyens »
    • les fines particules ou particules ayant une dimension inférieure à 3 mm appelées « fins »
Le fractionnement granulométrique peut dans certains cas être limité à deux fractions : les supérieures à 3 mm et les inférieures à 3 mm. Les coupures granulométriques à 3 et 5 mm peuvent également varier en fonction des conditions opératoires, de la nature des piles à l'entrée de l'unité et des impératifs fixés par la qualité des produits finis ou de la conduite de la table densimétrique.
Les coupures peuvent alors être définies à 1, 2, 3, 4, ... ou 20 mm.
  • une séparation qualitative, en deux étapes, des particules appelées « gros »:
    • un fractionnement densimétrique (table à air ou jigging) qui sépare les « gros » en trois catégories : 1) les éléments qualifiés de « lourds » tels que les fragments de zinc. de laiton, d'électrodes en carbone. 2) les éléments qualifiés de « légers » tels que les plastiques, les petits fragments métalliques et d'électrodes en carbone et 3) les éléments « très légers » tels que papier, cartons, ....
    • un fractionnement par Courants de Foucault (CDF) des éléments qualifiés de « légers » en éléments non-métalliques appelés « plastiques ». composés majoritairement de fragments de plastiques issus des carcasses des piles et de petits morceaux de carbone, et en éléments métalliques non-ferreux appelés « non-ferreux ». Ce type de fractionnement est également appliqué aux « lourds », de façon à séparer les pièces métalliques qui seront mélangées avec les « non-ferreux » issus du fractionnement des « légers ». des pièces non-métalliques telles que les électrodes en carbone, les morceaux de bakélites lourdes, ...que nous appellerons « rebus ».
L'ensemble des fractions produites peut donc se classifier comme suit :
  1. a) les « fins» : particules de plus petites dimensions ou inférieures à 3 mm
  2. b) les « moyens » : particules de dimensions intermédiaires ou comprises entre 3 et 5 mm. Cette fraction peut être inexistante si le criblage se limite à deux fractions.
  3. c) les « rébus » : particules de plus grandes dimensions ou supérieures à 3 ou 5 mm obtenues par séparation densimétrique (fraction lourde) et dont on a extrait les métaux par Courants de Foucault.
  4. d) les « non-ferreux » : particules de plus grandes dimensions ou supérieures à 3 ou 5 mm obtenues par la séparation densimétrique et extraites des « lourds » et/ou des « légers » par les Courants de Foucault (CDF).
  5. e) les « plastiques » : particules de plus grandes dimensions ou supérieures à 3 ou 5 mm obtenues par la séparation densimétrique (fraction légère) et dont on a extrait les métaux par Courants de Foucault.
  6. f) les « papiers » : particules de plus grandes dimensions ou supérieures à 3 ou 5 mm obtenues par la séparation densimétrique (fraction très légère).
  7. g) les « ferreux » : particules magnétiques de toutes dimensions séparées des autres fractions par son tambour magnétique ou un overband.
The first phase is in two stages.
The first step consists of manual sorting on conveyor belts, ensuring the removal of foreign bodies and unwanted batteries.
The second step is the mechanical screening of the mass for the recovery of the button cells.
At the end of the first phase, we have on the one hand. alkaline and salt batteries and secondly button cells, foreign bodies and other unwanted batteries which are directed to suitable treatment channels.
The second phase consists of the mechanical treatment of batteries comprising the following operations
  • mechanical grinding of batteries; this grinding, dry, is carried out by a crusher / crusher which can be either a rotary mill with hammers or moving bars, a percussion mill or a shredder mill. In fact. Any type of grinder can be chosen. provided that it reduces the piles in fragments from 0 to 15/20 mm.
  • the magnetic separation of the ground material by means of either an overband or a magnetic drum to extract the fragments of ferrous metals which will be called later "ferrous".
  • granulometric fractionation of the debris mill; the crushed food is divided into three categories:
    • particles larger than or larger than 5 mm called "fat"
    • particles of intermediate size or between 3 and 5 mm called "means"
    • fine particles or particles having a dimension of less than 3 mm referred to as "fine"
Granulometric fractionation may in some cases be limited to two fractions: those greater than 3 mm and those smaller than 3 mm. Particle size cuts at 3 and 5 mm can also vary depending on the operating conditions, the nature of the batteries at the inlet of the unit and the requirements imposed by the quality of the finished products or the conduct of the densimetric table.
The cuts can then be set to 1, 2, 3, 4, ... or 20 mm.
  • a qualitative separation, in two stages, of particles called "big":
    • a densimetric fractionation (air table or jigging) which separates the "big" into three categories: 1) the elements described as "heavy" such as zinc fragments. brass, carbon electrodes. 2) the elements described as "light" such as plastics, small fragments metal and carbon electrodes and 3) "very light" elements such as paper, cardboard, ....
    • Eddy current fractionation (FDC) of elements described as "light" in non-metallic elements called "plastics". consisting mainly of plastic fragments from battery carcasses and small pieces of carbon, and non-ferrous metal elements called "non-ferrous". This type of fractionation is also applied to "heavy", so as to separate the metal parts that will be mixed with "non-ferrous" from the fractionation of "light". non-metallic parts such as carbon electrodes, heavy bakelite pieces, ... which we will call "rebus".
All the fractions produced can therefore be classified as follows:
  1. a) "ends": particles smaller than or equal to 3 mm
  2. (b) 'means' means particles of intermediate size or between 3 and 5 mm. This fraction may be non-existent if the screening is limited to two fractions.
  3. (c) 'rebus' means particles of larger size or larger than 3 or 5 mm obtained by densimetric separation (heavy fraction) and from which the metals have been extracted by eddy currents.
  4. d) "non-ferrous": particles larger than or larger than 3 or 5 mm obtained by densimetric separation and extracted from "heavy" and / or "light" by eddy currents (FDC).
  5. (e) "plastics" means particles of larger size or greater than 3 or 5 mm obtained by the densimetric separation (light fraction) and from which the metals have been extracted by eddy currents.
  6. f) "papers": particles larger than or larger than 3 or 5 mm obtained by densimetric separation (very light fraction).
  7. (g) 'Ferrous' means magnetic particles of any size separated from other fractions by its magnetic drum or overband.

La phase trois comporte le traitement physique et/ou physico-chimique de certaines fractions. D'autres sont directement valorisées.
Les « ferreux » -fraction g- sont séparés mécaniquement des fines particules non-magnétiques qui pourraient encore s'y trouver. Cette séparation pourra se faire par criblage ou par soufflage/dépoussiérage. Cette séparation est facultative. Les métaux ferreux, éventuellement dépoussiérés, sont valorisés tels quels vers la sidérurgie via le circuit des récupérateurs de ferraille.
Les « non-ferreux » -fraction d- sont valorisés vers la métallurgie. l'hydrométallurgie ou le circuit des récupérateurs/recycleurs de métaux non-ferreux.
Les « plastiques » -fraction e- sont lavés dans un mélange d'acides sulfurique et nitrique, puis rincés plusieurs fois à l'eau et enfin égouttés. Après ce traitement, les « plastiques » propres sont valorisés tels quels ou après un rebroyage suivant la filière à laquelle ils sont destinés.
Les « moyens » -fraction b-. s'ils existent, sont éventuellement rebroyés pour être intégrés aux « fins » -fraction a-. Le groupe appelé « Black Mass ». en raccourci « BM », comprend ainsi les « fins » -fraction a-, les « moyens » rebroyés fraction b- et les poussières récupérées dans le système d'aspiration et de dépoussiérage de l'installation.
Ce groupe « BM » est soumis à un traitement hydrométallurgique permettant l'extraction et la récupération de ses très hautes teneurs en zinc et manganèse.
Il comprend les étapes suivantes :

  • la « BM » est d'abord lavée dans une solution de soude caustique, filtrée, et ensuite rincée à l'eau, une ou plusieurs fois, afin d'en extraire les chlorures. l' ammonium, le potassium et les autres sels solubles
  • l'attaque acide de la « BM » lavée par une solution d'acide sulfurique. en présence de fer métallique (poudre, copeaux, ...). pour mettre en solution le zinc et le manganèse présent sous la valence 2 -. La fraction de manganèse mise en solution lors de cette étape dépend du degré d'usure des piles traitées
  • la réduction de la pulpe ainsi obtenue, par du peroxyde d'hydrogène et en présence d'un antimousse, pour solubiliser le manganèse résiduaire constitué de MnO2 (valence 4+).
  • l'ajustement du pH par l'ammoniaque, l'oxyde de zinc ou l'oxyde de manganèse
  • la floculation de la pulpe
  • la filtration de la pulpe permettant de séparer une solution riche en sulfates de zinc et de manganèse et un résidu non-valorisable. éliminé comme déchet ultime après stabilisation.
  • la purification de la solution de sulfates qui comprend les opérations suivantes
    1. a) l'ajustement du pH par H2SO4
    2. b) la cémentation du cuivre, du cadmium, du mercure et du plomb par de la poudre de zinc et l'élimination des céments par filtration
    3. c) la complexation du nickel par l'éthylxanthate de sodium ou de potassium après réajustement du pH si nécessaire et son élimination par filtration
  • la valorisation du zinc et du manganèse compris dans la solution épurée soit par la valorisation de la solution elle-même, soit par précipitation sous forme d'un de leurs sels et la séparation de ceux-ci par filtration.
Phase three involves the physical and / or physicochemical treatment of certain fractions. Others are directly valued.
The "ferrous" fraction g- is mechanically separated from the non-magnetic fine particles that might still be there. This separation may be by screening or by blowing / dusting. This separation is optional. Ferrous metals, which may have been dusted off, are recycled as they are to the iron and steel industry via the scrap metal recycling circuit.
"Non-ferrous" -fraction d- are valued towards metallurgy. hydrometallurgy or the recycling / recycling circuit of non-ferrous metals.
The "plastics" -fraction e- are washed in a mixture of sulfuric and nitric acids, then rinsed several times with water and finally drained. After this treatment, the clean "plastics" are recovered as is or after a regrinding according to the die for which they are intended.
The "means" -fraction b-. if they exist, are eventually regrinded to be integrated in the "ends" -fraction a-. The group called "Black Mass". shorthand "BM", thus includes the "ends" -fraction a-, the "means" regrinded fraction b- and the dust recovered in the system of suction and dedusting of the installation.
This "BM" group is subjected to a hydrometallurgical treatment allowing the extraction and the recovery of its very high contents in zinc and manganese.
It includes the following steps:
  • the "BM" is first washed in a solution of caustic soda, filtered, and then rinsed with water, one or more times, in order to extract the chlorides. ammonium, potassium and other soluble salts
  • the acid attack of the "BM" washed with a sulfuric acid solution. in the presence of metallic iron (powder, chips, ...). to put in solution the zinc and the manganese present under the valence 2 -. The fraction of manganese dissolved in this step depends on the degree of wear of the treated cells
  • the reduction of the pulp thus obtained, with hydrogen peroxide and in the presence of an antifoam, to solubilize the residual manganese consisting of MnO 2 (valence 4+).
  • pH adjustment with ammonia, zinc oxide or manganese oxide
  • flocculation of the pulp
  • filtration of the pulp to separate a solution rich in sulfates of zinc and manganese and a non-recoverable residue. eliminated as ultimate waste after stabilization.
  • the purification of the sulphate solution which includes the following operations
    1. a) pH adjustment by H 2 SO 4
    2. b) the cementation of copper, cadmium, mercury and lead with zinc powder and the removal of the elements by filtration
    3. c) the complexation of the nickel with sodium or potassium ethylxanthate after readjustment of the pH if necessary and its elimination by filtration
  • the valorization of zinc and manganese included in the purified solution either by the valorization of the solution itself, or by precipitation in the form of one of their salts and the separation of these by filtration.

Il est évident que le procédé permet également de traiter tout matériau pouvant intégrer en quelques points que ce soit le processus décrit ci-dessus.
Dans le cas de la production d'une « BM » pauvre en MnO2, le procédé peut être modifié comme suit :

  • la réduction de la pulpe est omise
  • l'ajustement du pH avant floculation se fait avec de la « BM » lavée
  • la purification comprend alors
    1. a) la précipitation du fer au phosphate de sodium
    2. b) la cémentation du cuivre, du mercure et du plomb à la poudre de zinc après réajustement du pH
    3. c) l'élimination du nickel par complexation à l'éthylxanthate de sodium ou de potassium
  • la valorisation du zinc et du manganèse
It is obvious that the method also makes it possible to treat any material that can integrate at any point whatever the process described above.
In the case of the production of a "BM" poor in MnO 2 , the process can be modified as follows:
  • the reduction of the pulp is omitted
  • pH adjustment before flocculation is done with washed "BM"
  • purification then includes
    1. a) the precipitation of sodium phosphate iron
    2. b) the cementation of copper, mercury and lead to the zinc powder after readjustment of the pH
    3. c) elimination of nickel by complexation with sodium or potassium ethylxanthate
  • the valorization of zinc and manganese

La figure 1 représente le diagramme des opérations de tri.
La figure 2 représente le diagramme des traitements mécaniques et physiques.
La figure 3 représente le diagramme du traitement physico-chimique.
La figure 4 représente le diagramme de l'unité de tri et de traitement mécanique.
La figure 5 représente le diagramme de l'unité de lavage acide des matières plastiques.
La figure 6 représente le diagramme de l'unité d'extraction et de valorisation du zinc et du manganèseThe figure 1 represents the diagram of the sorting operations.
The figure 2 represents the diagram of mechanical and physical treatments.
The figure 3 represents the physico-chemical treatment diagram.
The figure 4 represents the diagram of the sorting and mechanical processing unit.
The figure 5 represents the diagram of the acidic washing unit of plastics.
The figure 6 represents the diagram of the zinc and manganese extraction and recovery unit

1- L'unité de tri et de traitement mécanioue (figure 4)1- The sorting and mechanical treatment unit (FIG. 4)

Cette unité comprend les éléments suivants :

  1. a) une trémie d'alimentation 4.1
  2. b) une bande transporteuse de triage manuel 4.2 qui passe par une cabine de triage 4.3 où sont extraits les corps étrangers et les piles indésirables (A)
  3. c) un crible vibrant 4.4 de séparation des piles boutons (B)
  4. d) une bande transporteuse d'alimentation de la trémie d'entrée du broyeur 4.5
  5. e) une trémie de stockage intermédiaire 4.6
  6. f) un vibrant balourdé d'alimentation automatique du broyeur 4.7
  7. g) un broyeur/concasseur 4.8
  8. h) un petit vibrant de désalimentation du broyeur 4.9
  9. i) une bande transporteuse d'alimentation du séparateur magnétique 4.10
  10. j) un vibrant d'alimentation du séparateur magnétique 4.11
  11. k) un tambour magnétique de séparation des matières ferreuses 4.12
  12. l) un couloir tubulaire vibrant 4.14 pour amener les matières magnétiques vers un crible oscillant de dépoussiérage
  13. m) un crible oscillant de dépoussiérage des matières magnétiques 4.15 permettant d'obtenir des pièces ferreuses (C) exemptes des dernières contaminations laissées par les constituants internes de la pile. Ces derniers sont récupérés sous forme d'une fraction très fine (D) et ajoutés à la « BM »
  14. n) un crible oscillant pour les matières non magnétiques 4.13. Ces dernières sont divisées en trois fractions :
    • les « fins » (E)
    • les « moyens » (F)
    • les « gros »
  15. o) une bande transporteuse d'alimentation 4.16 des matières criblées non magnétiques appelées « gros » vers le séparateur densimétrique
  16. p) un séparateur densimétrique « table à secousses » ou jigging 4.17 permettant de fractionner les « gros » en « lourds » (H), en « légers » (G) et en « très légers » (J)
  17. q) un séparateur à Courants de Foucault (CDF) qui divise les « légers » et les « lourds » en « plastiques », « non-ferreux » et « rebus »(non représenté)
  18. r) une installation de dépoussiérage comprenant :
    • un cyclone de pré-séparation 4.18
    • un filtre à manches 4.19
    qui permet de récupérer les poussières (I) produites lors du fonctionnement de l'installation.
This unit includes the following elements:
  1. a) a feed hopper 4.1
  2. b) a manual sorting conveyor belt 4.2 which passes through a sorting cabin 4.3 where foreign bodies and unwanted piles are extracted (A)
  3. c) a vibrating screen 4.4 for separating the button cells (B)
  4. d) a conveyor belt feeding the crusher inlet hopper 4.5
  5. e) an intermediate storage hopper 4.6
  6. f) A vibrated vibrator feeding automatic grinder 4.7
  7. g) a crusher / crusher 4.8
  8. h) a small vibrating feeder from the crusher 4.9
  9. i) a conveyor belt feeding the magnetic separator 4.10
  10. j) a feed vibrator of the magnetic separator 4.11
  11. k) a magnetic separation drum for ferrous materials 4.12
  12. l) a vibrating tubular corridor 4.14 to bring the magnetic materials to an oscillating screen of dedusting
  13. m) an oscillating screen of dedusting magnetic materials 4.15 to obtain ferrous parts (C) free of the latest contamination left by the internal components of the stack. These are recovered as a very fine fraction (D) and added to the "BM"
  14. n) an oscillating screen for non-magnetic materials 4.13. These are divided into three fractions:
    • the "ends" (E)
    • the "means" (F)
    • the fats "
  15. (o) a feeder conveyor belt 4.16 non-magnetic screened material called "coarse" to the densimetric separator
  16. p) a densimetric separator "jig table" or jigging 4.17 to split the "fat" into "heavy" (H), "light" (G) and "very light" (J)
  17. q) an eddy current separator (FDC) which divides "light" and "heavy" into "plastics", "non-ferrous" and "scrap" (not shown)
  18. r) a dedusting plant comprising:
    • a pre-separation cyclone 4.18
    • a bag filter 4.19
    which makes it possible to recover the dust (I) produced during the operation of the installation.

2- L'unité de traitement physico-chimique 2- Physicochemical treatment unit

L'unité de traitement physico-chimique peut se diviser en deux parties. La première est utilisée pour effectuer le lavage acide de la fraction appelée « plastiques ». La seconde permet le recyclage et la valorisation du zinc et du manganèse des piles par le traitement hydrométallurgique de la « BM ».The physico-chemical treatment unit can be divided into two parts. The first is used to carry out the acid wash of the fraction called "plastics". The second allows recycling and recovery of zinc and manganese batteries by the hydrometallurgical treatment of the "BM".

Le lavage acide des « plastiques » (figure 5) The acidic washing of "plastics" (Figure 5)

Cette unité comprend :

  1. a) une trémie d'alimentation 5.1
  2. b) un réacteur à fond conique 5.2 muni d'un agitateur mécanique et d'une grille perforée permettant la séparation des « plastiques » et de l'acide souillé ainsi que des premières eaux de lavage
  3. c) un réservoir de stockage pour le réactif « acide sulfurique et nitrique en mélange » 5.3
  4. d) un réservoir de stockage pour l'acide souillé et les eaux de rinçage en attente d'un traitement approprié 5.4
  5. e) un crible vibrant pour la séparation des dernières eaux de lavage et l'égouttage des « plastiques » propres 5.5
  6. f) un bassin de réception pour les dernières eaux de lavage et d'égouttage 5.6 avec retour vers la cuve de stockage 5.4
  7. g) un conteneur de stockage pour les « plastiques » propres 5.7
This unit includes:
  1. a) a feed hopper 5.1
  2. b) a conical bottom reactor 5.2 provided with a mechanical stirrer and a perforated grid allowing the separation of the "plastics" and the contaminated acid as well as the first washing water
  3. (c) a storage tank for the "mixed sulfuric and nitric acid" reagent 5.3
  4. (d) a storage tank for soiled acid and rinsing water awaiting appropriate treatment 5.4
  5. e) a vibrating screen for the separation of the last wash water and the draining of clean "plastics" 5.5
  6. f) a receiving basin for the last wash and drain water 5.6 with return to the storage tank 5.4
  7. g) a storage container for clean "plastics" 5.7

L'extraction et la valorisation du zinc et du manganèse (figure 6) Extraction and recovery of zinc and manganese (Figure 6)

L'unité d'extraction se compose de :

  1. a) un poste de chargement comportant une trémie d'alimentation 6.1, suivie d'un émotteur 6.2. ou un délayeur destiné à recevoir soit la « BM ». soit les gâteaux issus du lavage basique
  2. b) des réacteurs à fond conique 6.3 et 6.3' munis d'une hélice broyeuse, destiné à la mise en suspension des produits émottés
  3. c) un réacteur à fond conique 6.4 muni d'un mélangeur mécanique, où s'opèrent le lavage alcalin.la lixiviation acide et la réduction de la pulpe
  4. d) un réservoir de stockage pour le réactif « acide sulfurique » 6.5
  5. e) un réservoir de stockage pour le réactif « eau oxygénée » 6.6
  6. f) un réservoir de stockage pour le réactif « soude caustique » 6.7
  7. g) un réservoir de stockage pour le réactif « ammoniaque » 6.8
  8. h) un réservoir tampon à fond conique 6.9 muni d'un mélangeur mécanique
  9. i) un réacteur pour la préparation du floculant 6.10
  10. j) un réacteur de floculation à fond conique 6.11 muni d'un mélangeur mécanique
  11. k) une unité de filtration 6.12 composée d'un filtre-presse, d'un système de compactage et d'un système de lavage des toiles
  12. l) un conteneur pour le stockage des gâteaux de filtre-presse 6.13
  13. m) réservoirs de stockage pour le filtrat à valoriser 6.14
  14. n) un réservoir de stockage pour les eaux résiduaires du lavage basique 6.15.
The extraction unit consists of:
  1. (a) a loading station with a feed hopper 6.1, followed by a shoveler 6.2. or a paymaster destined to receive either the "BM". either the cakes from the basic washing
  2. b) conical bottom reactors 6.3 and 6.3 'equipped with a crusher propeller, intended for suspending the jelly products
  3. c) a conical bottom reactor 6.4 equipped with a mechanical mixer, where the alkaline wash is carried out. acid leaching and reduction of the pulp
  4. d) a storage tank for the "sulfuric acid" reagent 6.5
  5. e) a storage tank for the "hydrogen peroxide" reagent 6.6
  6. f) a storage tank for the "caustic soda" reagent 6.7
  7. (g) a storage tank for the ammonia reagent 6.8
  8. (h) a conical bottom buffer tank 6.9 equipped with a mechanical mixer
  9. i) a reactor for the preparation of flocculant 6.10
  10. j) a flocculation reactor with a conical bottom 6.11 equipped with a mechanical mixer
  11. k) a 6.12 filter unit consisting of a filter press, a compaction system and a scrubbing system
  12. l) a container for the storage of filter press cakes 6.13
  13. m) storage tanks for the filtrate to be upgraded 6.14
  14. n) a storage tank for the waste water of the basic washing 6.15.

Claims (5)

  1. Process for recycling and valorisation of saline and alkaline batteries, comprising a series of three phases: a first phase wherein the batches of collected batteries are sorted, a second phase of mechanical treatment of the batteries, comprising the mechanical grinding of the batteries, the magnetic separation of the ground matter, the fractional sieving of the de-ironed ground matter and the qualitative separation of the so-called "large" particles and resulting into seven product fractions: "ferrous", "fines", "medium", "scraps", "non-ferrous", "plastics" and "paper"; and a third phase of physical or physical-chemical treatment of these fractions, the "ferrous" and "non-ferrous" parts fractions being valorised and the "plastics" fraction being washed in a mixture of sulphuric and nitric acids, rinsed and drained, characterised in that, in the third phase, the "medium" fraction is re-ground and integrated into the "fines" fraction to form a single group called "Black Mass", this group being subjected to a hydrometallurgical treatment comprising the following stages: firstly a caustic soda wash, a filtration and a rinse in order to extract the chlorides, the ammonium, the potassium and the other soluble salts; then an acid attack with a sulphuric acid solution in presence of metallic iron in order to dissolve the zinc and manganese; then a reduction by hydrogen peroxide in presence of an anti-froth for dissolving the residual manganese, the adjustment of pH by ammonia, zinc oxide or manganese oxide, the flocculation of the group, the filtration allowing the separation of a solution rich in zinc and manganese sulphates, the purification of the solution comprising the adjustment of the pH by H2SO4, the cementation of copper, cadmium, mercury and lead by zinc powder and the elimination of cements by filtration, and the complexing of nickel with sodium or potassium ethylxanthate after re-adjustment of the pH and its elimination by filtration and then the valorisation of the zinc and magnesium sulphates contained in the purified solution as they are or after precipitation.
  2. Process for the recycling and the valorisation of saline and alkaline batteries according to claim 1 characterised in that the reduction of the group is omitted, the adjustment of pH before flocculation is done with the washed products of the same group, and
    in that the purification comprises then the precipitation of iron with sodium phosphate, the cementation of the copper, mercury and the lead by zinc powder after re-adjustment of the pH, the elimination of nickel by complexing by sodium or potassium ethylxanthate and the anodising of the manganese.
  3. Process for the recycling and the valorisation of saline and alkaline batteries according
    to claim 1, characterised in that it uses a physico-chemical treatment unit which
    can be divided into two parts, the first one being used for carrying out the acid washing of the "plastics"
    fraction for valorising it as fuel, the second allowing recycling and valorisation
    of the high content of zinc and manganese in the batteries by the hydro-metallurgic treatment.
  4. Process for the recycling and the valorisation of saline and alkaline batteries according to
    claims 1 and 3 characterised in that it uses a unit for the acid washing of the "plastics"
    comprising a feed hopper (5.1), a reactor with a conical bottom (5.2), a storage vessel (5.3) for the mixed "sulphuric and nitric acid" reagent , a storage vessel (5.4)
    of the dirty acid and the rinsing water, a vibrating sieve (5.5): a reception basin (5.6) for the final washing and drainage water and a storage container (5.7) for clean "plastics".
  5. Process for the recycling and valorisation of saline and alkaline batteries according to
    claims 1 and 3, characterised in that it uses an extraction and valorisation unit for zinc
    and manganese comprising a feed hopper (6.1) for receiving products of the "Black Mass" group, a rake (6.2), reactors 6.3 and 6.3' with conical bottoms provided
    with a grinding blade, a reactor (6.4) with conical bottom provided with a mechanical
    mixer, a storage vessel (6.5) for the "sulphuric acid" reagent, a storage vessel (6.6) for
    the "peroxidated water" reagent, a storage vessel (6.7) for the "caustic soda" reagent, a storage vessel (6.8) for the "ammonia" reagent, a buffer vessel (6.9)
    with conical bottom and a mechanical mixer, a reactor (6.10) for the flocculent,
    a flocculation reactor (6.11), a unit (6.12) consisting of a filter press, a compacting system and a system for washing fabric, a storage container (6.13) for the filter press cakes and vessels (6.14) for the filtrate to be valorised and the effluent from the alkaline wash.
EP20010108707 2000-04-17 2001-04-06 Method for recycling and treating of salt and alkaline batteries Expired - Lifetime EP1148571B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE200000275 2000-04-17
BE2000/0275A BE1013311A4 (en) 2000-04-17 2000-04-17 Process for recycling and recovery of saline and alkaline batteries

Publications (2)

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EP1148571A1 EP1148571A1 (en) 2001-10-24
EP1148571B1 true EP1148571B1 (en) 2009-10-21

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AT (1) ATE446593T1 (en)
BE (1) BE1013311A4 (en)
DE (2) DE60140231D1 (en)
ES (1) ES2167287T3 (en)
PT (1) PT1148571E (en)

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CN102403554A (en) * 2011-11-10 2012-04-04 大连交通大学 Recycling method for positive electrode materials of waste lithium iron phosphate batteries
WO2019150005A1 (en) 2018-02-05 2019-08-08 Tracegrow Oy Processes for production of micronutrients from spent alkaline batteries
EP3750206A4 (en) * 2018-02-05 2021-11-03 Tracegrow Oy Processes for production of micronutrients from spent alkaline batteries

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BE1014406A3 (en) * 2001-10-01 2003-10-07 Erachem Europ Sociutu Anonyme Method of preparation of mixed oxide zinc manganese.
ITRM20040578A1 (en) * 2004-11-25 2005-02-25 Univ Roma PROCESS AND PLANT FOR THE TREATMENT OF EXHAUSTED PILE.
KR100975317B1 (en) * 2009-11-20 2010-08-12 한국지질자원연구원 Method for preparing manganese sulfate and zinc sulfate from waste batteries containing manganese and zinc
WO2011113860A1 (en) * 2010-03-16 2011-09-22 Akkuser Ltd Battery recycling method
IT1401628B1 (en) * 2010-08-10 2013-07-26 Fortom Chimica S R L PROCEDURE FOR THE RECOVERY OF CONSTITUTING MATERIALS BATTERIES, RECHARGEABLE LITHIUM CELLS AND / OR BATTERIES, AND USE OF RECOVERED CATHODIC MATERIAL
WO2012025568A2 (en) * 2010-08-24 2012-03-01 Akkuser Oy Metal ion recovery from battery waste
ITVI20110207A1 (en) * 2011-07-28 2013-01-29 Fortom Chimica S R L SHREDDER FOR THE SHREDDING OF BATTERIES, IN PARTICULAR PRIMARY LITHIUM BATTERIES, AND PROCEDURE FOR RECYCLING AND TREATMENT OF PRIMARY LITHIUM BATTERIES
ITMI20130366A1 (en) 2013-03-11 2014-09-12 Ambiente Ecologia S R L Soc It PROCESS FOR RECOVERY OF RAW MATERIALS.
CN103934102B (en) * 2014-02-25 2016-04-06 超威电源有限公司 A kind of lead powder reclaimer
CN104037468B (en) * 2014-06-05 2016-06-22 浙江工业大学 A kind of method reclaiming manganese and copper resource from waste and old lithium ion battery
FR3047420B1 (en) * 2016-02-10 2018-03-09 Commissariat A L'energie Atomique Et Aux Energies Alternatives SELECTIVE DISSOLUTION METHOD USING NON-IONIC SURFACTANT
CN108110362B (en) * 2017-12-21 2019-11-15 天齐锂业股份有限公司 The method of the ternary material precursor of zinc doping is synthesized by waste lithium cell recycling
CN110364777A (en) * 2019-07-17 2019-10-22 刘艳 Refuse battery method for innocent treatment and system

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CN102403554A (en) * 2011-11-10 2012-04-04 大连交通大学 Recycling method for positive electrode materials of waste lithium iron phosphate batteries
WO2019150005A1 (en) 2018-02-05 2019-08-08 Tracegrow Oy Processes for production of micronutrients from spent alkaline batteries
EP3750206A4 (en) * 2018-02-05 2021-11-03 Tracegrow Oy Processes for production of micronutrients from spent alkaline batteries
AU2019214459B2 (en) * 2018-02-05 2024-06-06 Tracegrow Oy Processes for production of micronutrients from spent alkaline batteries

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ES2167287T3 (en) 2010-03-26
DE60140231D1 (en) 2009-12-03
ES2167287T1 (en) 2002-05-16
EP1148571A1 (en) 2001-10-24
ATE446593T1 (en) 2009-11-15
DE1148571T1 (en) 2002-06-13
BE1013311A4 (en) 2001-11-06
PT1148571E (en) 2010-01-26

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